Tag Archives: Vladimir E. Bochenkov

Mechanism behind interaction of silver nanoparticles with the cells of the immune system

Scientists have come to a better understanding of the mechanism affecting silver nanoparticle toxicity according to an Aug. 30, 2016 news item on Nanowerk (Note: A link has been removed),

A senior fellow at the Faculty of Chemistry, MSU (Lomonosov Moscow State University), Vladimir Bochenkov together with his colleagues from Denmark succeeded in deciphering the mechanism of interaction of silver nanoparticles with the cells of the immune system. The study is published in the journal Nature Communications (“Dynamic protein coronas revealed as a modulator of silver nanoparticle sulphidation in vitro”).

‘Currently, a large number of products are containing silver nanoparticles: antibacterial drugs, toothpaste, polishes, paints, filters, packaging, medical and textile items. The functioning of these products lies in the capacity of silver to dissolve under oxidation and form ions Ag+ with germicidal properties. At the same time there are research data in vitro, showing the silver nanoparticles toxicity for various organs, including the liver, brain and lungs. In this regard, it is essential to study the processes occurring with silver nanoparticles in biological environments, and the factors affecting their toxicity,’ says Vladimir Bochenkov.

Caption: Increased intensity of the electric field near the silver nanoparticle surface in the excitation of plasmon resonance. Credit: Vladimir Bochenkov

Caption: Increased intensity of the electric field near the silver nanoparticle surface in the excitation of plasmon resonance. Credit: Vladimir Bochenkov

An Aug. 30, 2016 MSU press release on EurekAlert, which originated the news item, provides more information about the research,

The study is devoted to the protein corona — a layer of adsorbed protein molecules, which is formed on the surface of the silver nanoparticles during their contact with the biological environment, for example in blood. Protein crown masks nanoparticles and largely determines their fate: the speed of the elimination from the body, the ability to penetrate to a particular cell type, the distribution between the organs, etc.

According to the latest research, the protein corona consists of two layers: a rigid hard corona — protein molecules tightly bound with silver nanoparticles, and soft corona, consisting of weakly bound protein molecules in a dynamic equilibrium with the solution. Hitherto soft corona has been studied very little because of the experimental difficulties: the weakly bound nanoparticles separated from the protein solution easily desorbed (leave a particle remaining in the solution), leaving only the rigid corona on the nanoparticle surface.

The size of the studied silver nanoparticles was of 50-88 nm, and the diameter of the proteins that made up the crown — 3-7 nm. Scientists managed to study the silver nanoparticles with the protein corona in situ, not removing them from the biological environment. Due to the localized surface plasmon resonance used for probing the environment near the surface of the silver nanoparticles, the functions of the soft corona have been primarily investigated.

‘In the work we showed that the corona may affect the ability of the nanoparticles to dissolve to silver cations Ag+, which determine the toxic effect. In the absence of a soft corona (quickly sharing the medium protein layer with the environment) silver cations are associated with the sulfur-containing amino acids in serum medium, particularly cysteine and methionine, and precipitate as nanocrystals Ag2S in the hard corona,’ says Vladimir Bochenkov.

Ag2S (silver sulfide) famously easily forms on the silver surface even on the air in the presence of the hydrogen sulfide traces. Sulfur is also part of many biomolecules contained in the body, provoking the silver to react and be converted into sulfide. Forming of the nano-crystals Ag2S due to low solubility reduces the bioavailability of the Ag+ ions, reducing the toxicity of silver nanoparticles to null. With a sufficient amount of amino acid sulfur sources available for reaction, all the potentially toxic silver is converted into the nontoxic insoluble sulfide. Scientists have shown that what happens in the absence of a soft corona.

In the presence of a soft corona, the Ag2S silver sulfide nanocrystals are formed in smaller quantities or not formed at all. Scientists attribute this to the fact that the weakly bound protein molecules transfer the Ag+ ions from nanoparticles into the solution, thereby leaving the sulfide not crystallized. Thus, the soft corona proteins are ‘vehicles’ for the silver ions.

This effect, scientists believe, be taken into account when analyzing the stability of silver nanoparticles in a protein environment, and in interpreting the results of the toxicity studies. Studies of the cells viability of the immune system (J774 murine line macrophages) confirmed the reduction in cell toxicity of silver nanoparticles at the sulfidation (in the absence of a soft corona).

Vladimir Bochenkov’s challenge was to simulate the plasmon resonance spectra of the studied systems and to create the theoretical model that allowed quantitative determination of silver sulfide content in situ around nanoparticles, following the change in the absorption bands in the experimental spectra. Since the frequency of the plasmon resonance is sensitive to a change in dielectric constant near the nanoparticle surface, changes in the absorption spectra contain information about the amount of silver sulfide formed.

Knowledge of the mechanisms of formation and dynamics of the behavior of the protein corona, information about its composition and structure are extremely important for understanding the toxicity and hazards of nanoparticles for the human body. In prospect the protein corona formation can be used to deliver drugs in the body, including the treatment of cancer. For this purpose it will be enough to pick such a content of the protein corona, which enables silver nanoparticles penetrate only in the cancer cell and kill it.

Here’s a link to and a citation for the paper describing this fascinating work,

Dynamic protein coronas revealed as a modulator of silver nanoparticle sulphidation in vitro by Teodora Miclăuş, Christiane Beer, Jacques Chevallier, Carsten Scavenius, Vladimir E. Bochenkov, Jan J. Enghild, & Duncan S. Sutherland. Nature Communications 7,
Article number: 11770 doi:10.1038/ncomms11770 Published  09 June 2016

This paper is open access.

The Danish ‘Mini-mouth and wine

Denmark is not the first country that pops to mind when there’s mention of a nanosensor that mimics what happens in your mouth when you drink wine but that’s where the device was developed. From a Sept. 17, 2014 news item on ScienceDaily,

When wine growers turn their grapes into wine, they need to control a number of processes to bring out the desired flavour in the product that ends up in the wine bottle. An important part of the taste is known in wine terminology as astringency, and it is characteristic of the dry sensation you get in your mouth when you drink red wine in particular. It is the tannins in the wine that bring out the sensation that — otherwise beyond compare — can be likened to biting into an unripe banana. It is mixed with lots of tastes in the wine and feels both soft and dry.

Researchers at the Interdisciplinary Nanoscience Centre (iNANO ), Aarhus University, have now developed a nanosensor that is capable of measuring the effect of astringency in your mouth when you drink wine.

A Sept. 17, 2014 Aarhus University (Denmark) press release (also on EurekAlert), which originated the news item, provides a general description of the sensor,

… To put it simply, the sensor is a kind of mini-mouth that uses salivary proteins to measure the sensation that occurs in your mouth when you drink wine. The researchers are looking at how the proteins change in the interaction with the wine, and they can use this to describe the effect of the wine.

There is great potential in this – both for the wine producers and for research into the medicine of the future. Indeed, it is the first time that a sensor has been produced that not only measures the amount of proteins and molecules in your mouth when you drink wine, but also measures the effect of wine – or other substances – entering your mouth.

The wine producers’ perspective is introduced (from the news release),

The sensor makes it possible for wine producers to control the development of astringency during wine production because they can measure the level of astringency in the wine right from the beginning of the process. This can currently only be achieved when the wine is ready and only by using a professional tasting panel – with the associated risk of human inaccuracy. Using the sensor, producers can work towards the desired sensation of dryness before the wine is ready.

“We don’t want to replace the wine taster. We just want a tool that is useful in wine production. When you produce wine, you know that the finished product should have a distinct taste with a certain level of astringency. If it doesn’t work, people won’t drink the wine,” says PhD student Joana Guerreiro, first author of the scientific article in ACS NANO, which presents the sensor and its prospects.

Better Understanding of Astringency

There are many different elements in wine that create astringency, and this makes it difficult to measure because there are so many parameters. The sensor turns this upside down by measuring the molecules in your mouth instead.

“The sensor expands our understanding of the concept of astringency. The sensation arises because of the interaction between small organic molecules in the wine and proteins in your mouth. This interaction gets the proteins to change their structure and clump together. Until now, the focus has been on the clumping together that takes place fairly late in the process. With the sensor, we’ve developed a method that mimics the binding and change in the structure of the proteins, i.e. the early part of the process. It’s a more sensitive method, and it reproduces the effect of the astringency better,” says Joana Guerreiro.

There are also some technical details in the news release,

Quite specifically, the sensor is a small plate coated with nanoscale gold particles. On this plate, the researchers simulate what happens in your mouth by first adding some of the proteins contained in your saliva. After this they add the wine. The gold particles on the plate act as nano-optics and make it possible to focus a beam of light below the diffraction limit so as to precisely measure something that is very small – right down to 20 nanometres. This makes it possible to study and follow the proteins, and to see what effect the wine has. It is thereby possible to see the extent to which the small molecules have to bind together for the clumping effect on the protein to be set off.

The technique in itself is not new. What is new is using it to create a sensor that can measure an effect rather than just a number of molecules. In this case, the effect is the dry sensation you get in your mouth when you drink wine. However, it is also possible to use the sensor to measure other effects.

Here’s a look at the Mini-mouth,

PhD student Joana Guerreiro has taken part in developing a sensor, which - by using nanoscience - can measure how we experience the feeling of dryness in wine. Photo: Lars Kruse, Aarhus University.

PhD student Joana Guerreiro has taken part in developing a sensor, which – by using nanoscience – can measure how we experience the feeling of dryness in wine. Photo: Lars Kruse, Aarhus University.

Here’s a link to and a citation for the paper,

Multifunctional Biosensor Based on Localized Surface Plasmon Resonance for Monitoring Small Molecule–Protein Interaction by Joana Rafaela Lara Guerreiro, Maj Frederiksen, Vladimir E. Bochenkov, Victor De Freitas, Maria Goreti Ferreira Sales, and Duncan Steward Sutherland. ACS Nano, 2014, 8 (8), pp 7958–7967 DOI: 10.1021/nn501962y Publication Date (Web): July 8, 2014

Copyright © 2014 American Chemical Society

This paper is behind a paywall.

ETA Sept. 19, 2014: Dexter Johnson provides some insight into the field of ‘artificial mouths’ in his Sept. 18, 2014 posting (Nanoclast blog on the IEEE [Institute of Electrical and Electronics Engineers] about the work in Denmark.